有機(jī)含氮化合物(8)ppt課件

1、Chapter 13 Organic Compounds Containing Nitrogen有機(jī)含氮化合物RNO2NO2RCNORRCCOONRRCNRCRNOHRNH2RNHRRNRRRNRRRXRNRRROHArN2XCH2N2NNArAr硝基化合物硝基化合物酰胺酰胺 腈腈肟肟胺胺重氮和偶氮化合物重氮和偶氮化合物 含氮有機(jī)物含氮有機(jī)物 硝基化合物 Nitro Compunds酰胺 Amides腈 Nitriles肟 Oximes胺 Amines 重氮和偶氮化合物 Diazonium Salts & Azo compoundsAmine(胺胺)NH3 胺(Amine) 銨 銨鹽

2、(Ammonium Salt) 氨(Ammonia)RNH2RNHRRNRRRNRRRXRNRRROH 季胺鹽(Quaternary Ammonium Salt)根據(jù)根據(jù)N上所連烴基的種類上所連烴基的種類脂肪胺脂肪胺芳香胺芳香胺芳脂胺芳脂胺CH3NH2NH2CH2NH2一一. Classification & Naming:根據(jù)根據(jù)N上所連烴基的數(shù)目上所連烴基的數(shù)目RNH2R2NHR3NR4N+1胺 伯胺Primary Amines2胺 仲胺Secondary Amines3胺 叔胺Tertiary Amines 4胺 季銨鹽)Quaternary Ammonium SaltClass

3、ification & Naming根據(jù)分子中胺基的數(shù)目根據(jù)分子中胺基的數(shù)目一元胺一元胺多元胺多元胺胺的分級(jí)與鹵代烴、醇不同胺的分級(jí)與鹵代烴、醇不同 ！(CH3)3C-OH3醇醇(CH3)3C-NH21胺胺Classification & Naming(CH3)3CX3o鹵代烴鹵代烴(CH3)2NHdimethyl amineNH2aniline 苯胺NHCH3N-methyl anilineCH3-NH2methyl amine 甲基胺CH3CH2NH2ethyl amine 乙胺Classification & NamingCH3CH2CH2CHCHCH3CH2NH

4、2N(CH3)23-胺甲基胺甲基-2-N, N-二甲胺基己烷二甲胺基己烷C6H5NH3+Cl-氯化苯銨氯化苯銨CH3CH2NHCHCH2CH3CH2CH2CH2CH2CH3Classification & NamingHOCH2CH2NH2CH3CHNCH3CO2HHSO2HH2N(CH3CH2NH3)2SO4-(CH3)4N+Cl-3-(N-乙胺基乙胺基)庚烷庚烷2-氨基乙醇氨基乙醇 -(N-甲胺基甲胺基)丙酸丙酸對(duì)氨基苯磺酸對(duì)氨基苯磺酸氯化四甲銨氯化四甲銨硫酸乙銨硫酸乙銨二二 .Structure & Isomerism:SP3NH3CHHNH3CCH3CH3NHHSP3S

5、P3“ SP2 Structure & Isomerism胺的對(duì)映體的轉(zhuǎn)變胺的對(duì)映體的轉(zhuǎn)變構(gòu)型翻轉(zhuǎn)，能壘較低，翻轉(zhuǎn)速度較快構(gòu)型翻轉(zhuǎn)，能壘較低，翻轉(zhuǎn)速度較快N上不同的取代上不同的取代手性氮手性氮對(duì)映異構(gòu)體對(duì)映異構(gòu)體 ？自動(dòng)外消旋化，不可拆分自動(dòng)外消旋化，不可拆分Structure & Isomerism 氮在環(huán)內(nèi)，翻轉(zhuǎn)受阻氮在環(huán)內(nèi)，翻轉(zhuǎn)受阻 季銨鹽季銨鹽 不能進(jìn)展氮的翻轉(zhuǎn)不能進(jìn)展氮的翻轉(zhuǎn) 可分別出穩(wěn)定的旋光異構(gòu)體可分別出穩(wěn)定的旋光異構(gòu)體胺的對(duì)映體的轉(zhuǎn)變胺的對(duì)映體的轉(zhuǎn)變Structure & IsomerismH3CNNTroger 堿S-R- 構(gòu)成構(gòu)成N氧化物，不能翻轉(zhuǎn)氧

6、化物，不能翻轉(zhuǎn) PhNC2H5CH3ONH5C2CH2CHPhCH3CH2NC2H5CHCH2PhCH3H2C三三. Preparation of AaminesPreparation by Nucleolic Substitution1、胺的烷基化、胺的烷基化RX +NH3RNH2RX- HXR2NHRX- HXR3NRX- HXR4N+X-1 胺胺2胺胺3胺胺4胺胺反響產(chǎn)物復(fù)雜反響產(chǎn)物復(fù)雜如何控制產(chǎn)物在如何控制產(chǎn)物在1 胺？胺？采用該法合成胺，哪一種鹵代烷不適用？采用該法合成胺，哪一種鹵代烷不適用？NH2+CH2ClNaHCO3(aq.)8587%NHCH29095 oC+NH2CH3CH

7、2Cl (過(guò)量)NCH2CH3CH2CH3芳香胺芳香胺 Preparation of Aamines3、Gabriel 合成法制備合成法制備1胺胺EthanolNHOOKOHNOOKNOORRX2KOHH2NNH2NOOR+COOKCOOKRNH2OONHNH+RNH22、芳香鹵代烴的胺解、芳香鹵代烴的胺解+ClNO2O2NNH3NH2NO2O2NClNO2+CH3NH2NO2NHCH3EtOH160 oC Preparation of AaminesPreparation by ReductionNO21. Zn /HCl 2. OH-or H2/PtNH2NO2NO2NH4SHNO2NH2

8、1. 硝基化合物硝基化合物CH3CH2BrNaN3EthanolCH3CH2NNN(1) LiAlH4(2) H2OCH3CH2NH21 胺胺2. 腈腈RCNLiAlH4RCH2NH23. 酰胺酰胺RCNR2OLiAlH4RCH2NR24. 肟肟OH2NOHNOHNaC2H5OHNH25. Alkyl Azide 疊氮物疊氮物 Preparation of Aamines6、羰基化合物的復(fù)原胺化、羰基化合物的復(fù)原胺化 (Reductive Amination)RCH (R)O+RRNH2H2/NiRCHH(R)NRRRCH (R)NRR+H2/NiCH3CH=ONH3CH3CH2NH2NH31

9、 胺胺+H2/NiCH3CH2CHOCH3CH2NH2CH3CH2CH2NHCH2CH31 胺胺2 胺胺2 胺胺3 胺胺+RNH22H2CO+ 2HCOOHRN(CH3)21 胺的二甲基化胺的二甲基化 Preparation of AaminesPreparation by Rearrangements1、Hofmann Rearrangements Hofmann 重排，降解重排，降解CH3(CH2)4CNH2OBr2OH-CH3(CH2)3CH2NH2RCNHHOBr2OH-RCNHBrOOH -RCNBrOOCNROH-RNH2異氰酸酯異氰酸酯機(jī)理機(jī)理 Preparation of Aa

10、minesCCONH2H5C2H3CHBr2/OH-CNH2H5C2H3CHR-2-甲基丁酰胺甲基丁酰胺R-2-甲基丁胺甲基丁胺CCH5C2H3CHONBrCNOBrCH5C2CH3H-+CNH5C2H3CHCO三元環(huán)過(guò)渡態(tài)三元環(huán)過(guò)渡態(tài)構(gòu)型堅(jiān)持構(gòu)型堅(jiān)持SN2Stereochemistry Preparation of Aamines2、Curtius & Schmidt RearrangementsRCOCl+NaN3RCOOH+NaN3RCNNNO-N2NCORH2ORNH2酰疊氮化合物酰疊氮化合物CurtiusSchmidtH2OCClONaN3CN3ONH260%H3O+NaN3ClCO2HClNH275%Preparation by Mannich reaction Preparation of AaminesCH3CCH3O+CH2O+(C2H5)2NH2+Cl-CH3CCH2CH2N+H(C2H5)2Cl-O6675%+ CH2O+(CH3)2NH2+Cl-CCH3OCCH2CH2N+H(CH3)2Cl-O70% -胺基酮胺基酮 -H 酮酮甲醛甲醛胺鹽胺鹽酸性水、醇溶液酸